This invention relates to an electrophoretic medium with improved image stability, and to an electrophoretic display incorporating such an electrophoretic medium. More specifically, this invention relates to an electrophoretic medium and display which allow improved image stability without unacceptable increases in the switching time or the drive voltage of the display.
The terms “bistable” and “bistability” are used herein in their conventional meaning in the art to refer to displays comprising display elements having first and second display states differing in at least one optical property, and such that after any given element has been driven, by means of an addressing pulse of finite duration, to assume either its first or second display state, after the addressing pulse has terminated, that state will persist for at least several times, for example at least four times, the minimum duration of the addressing pulse required to change the state of the display element. It is shown in U.S. Pat. No. 7,170,670 that some particle-based electrophoretic displays capable of gray scale are stable not only in their extreme black and white states but also in their intermediate gray states, and the same is true of some other types of electro-optic displays. This type of display is properly called “multi-stable” rather than bistable, although for convenience the term “bistable” may be used herein to cover both bistable and multi-stable displays.
Particle-based electrophoretic displays have been the subject of intense research and development for a number of years. In this type of display, a plurality of charged particles move through a fluid under the influence of an electric field. Electrophoretic displays can have attributes of good brightness and contrast, wide viewing angles, state bistability, and low power consumption when compared with liquid crystal displays. In such electrophoretic displays, an optical property is changed by application of the electric field; this optical property is typically color perceptible to the human eye, but may be another optical property, such as optical transmission, reflectance, luminescence or, in the case of displays intended for machine reading, pseudo-color in the sense of a change in reflectance of electromagnetic wavelengths outside the visible range. Nevertheless, problems with the long-term image quality of these displays have prevented their widespread usage. For example, particles that make up electrophoretic displays tend to settle, resulting in inadequate service-life for these displays.
Numerous patents and applications assigned to or in the names of the Massachusetts Institute of Technology (MIT) and E Ink Corporation have recently been published describing encapsulated electrophoretic media. Such encapsulated media comprise numerous small capsules, each of which itself comprises an internal phase containing electrophoretically-mobile particles suspended in a liquid suspending medium, and a capsule wall surrounding the internal phase. Typically, the capsules are themselves held within a polymeric binder to form a coherent layer positioned between two electrodes. Encapsulated media of this type are described, for example, in U.S. Pat. Nos. 5,930,026; 5,961,804; 6,017,584; 6,067,185; 6,118,426; 6,120,588; 6,120,839; 6,124,851; 6,130,773; 6,130,774; 6,172,798; 6,177,921; 6,232,950; 6,249,271; 6,252,564; 6,262,706; 6,262,833; 6,300,932; 6,312,304; 6,312,971; 6,323,989; 6,327,072; 6,376,828; 6,377,387; 6,392,785; 6,392,786; 6,413,790; 6,422,687; 6,445,374; 6,445,489; 6,459,418; 6,473,072; 6,480,182; 6,498,114; 6,504,524; 6,506,438; 6,512,354; 6,515,649; 6,518,949; 6,521,489; 6,531,997; 6,535,197; 6,538,801; 6,545,291; 6,580,545; 6,639,578; 6,652,075; 6,657,772; 6,664,944; 6,680,725; 6,683,333; 6,704,133; 6,710,540; 6,721,083; 6,724,519; 6,727,881; 6,738,050; 6,750,473; 6,753,999; 6,816,147; 6,819,471; 6,822,782; 6,825,068; 6,825,829; 6,825,970; 6,831,769; 6,839,158; 6,842,167; 6,842,279; 6,842,657; 6,864,875; 6,865,010; 6,866,760; 6,870,661; 6,900,851; 6,922,276; 6,950,200; 6,958,848; 6,967,640; 6,982,178; 6,987,603; 6,995,550; 7,002,728; 7,012,600; 7,012,735; 7,023,420; 7,030,412; 7,030,854; 7,034,783; 7,038,655; 7,061,663; 7,071,913; 7,075,502; 7,075,703; 7,079,305; 7,106,296; 7,109,968; 7,110,163; 7,110,164; 7,116,318; 7,116,466; 7,119,759; 7,119,772; 7,148,128; 7,167,155; 7,170,670; 7,173,752; 7,176,880; 7,180,649; 7,190,008; 7,193,625; 7,202,847; 7,202,991; 7,206,119; 7,223,672; 7,230,750; 7,230,751; 7,236,790; and 7,236,792; and U.S. Patent Applications Publication Nos. 2002/0060321; 2002/0090980; 2003/0011560; 2003/0102858; 2003/0151702; 2003/0222315; 2004/0094422; 2004/0105036; 2004/0112750; 2004/0119681; 2004/0136048; 2004/0155857; 2004/0180476; 2004/0190114; 2004/0196215; 2004/0226820; 2004/0257635; 2004/0263947; 2005/0000813; 2005/0007336; 2005/0012980; 2005/0017944; 2005/0018273; 2005/0024353; 2005/0062714; 2005/0067656; 2005/0099672; 2005/0122284; 2005/0122306; 2005/0122563; 2005/0134554; 2005/0151709; 2005/0152018; 2005/0156340; 2005/0179642; 2005/0190137; 2005/0212747; 2005/0213191; 2005/0219184; 2005/0253777; 2005/0280626; 2006/0007527; 2006/0024437; 2006/0038772; 2006/0139308; 2006/0139310; 2006/0139311; 2006/0176267; 2006/0181492; 2006/0181504; 2006/0194619; 2006/0197736; 2006/0197737; 2006/0197738; 2006/0202949; 2006/0223282; 2006/0232531; 2006/0245038; 2006/0256425; 2006/0262060; 2006/0279527; 2006/0291034; 2007/0035532; 2007/0035808; 2007/0052757; 2007/0057908; 2007/0069247; 2007/0085818; 2007/0091417; 2007/0091418; 2007/0097489; 2007/0109219; 2007/0128352; and 2007/0146310; and International Applications Publication Nos. WO 00/38000; WO 00/36560; WO 00/67110; and WO 01/07961; and European Patents Nos. 1,099,207 B1; and 1,145,072 B1.
Many of the aforementioned patents and applications recognize that the walls surrounding the discrete microcapsules in an encapsulated electrophoretic medium could be replaced by a continuous phase, thus producing a so-called polymer-dispersed electrophoretic display, in which the electrophoretic medium comprises a plurality of discrete droplets of an electrophoretic fluid and a continuous phase of a polymeric material, and that the discrete droplets of electrophoretic fluid within such a polymer-dispersed electrophoretic display may be regarded as capsules or microcapsules even though no discrete capsule membrane is associated with each individual droplet; see for example, the aforementioned U.S. Pat. No. 6,866,760. Accordingly, for purposes of the present application, such polymer-dispersed electrophoretic media are regarded as sub-species of encapsulated electrophoretic media.
A related type of electrophoretic display is a so-called “microcell electrophoretic display”. In a microcell electrophoretic display, the charged particles and the fluid are not encapsulated within microcapsules but instead are retained within a plurality of cavities formed within a carrier medium, typically a polymeric film. See, for example, U.S. Pat. Nos. 6,672,921 and 6,788,449, both assigned to Sipix Imaging, Inc.
Although electrophoretic media are often opaque (since, for example, in many electrophoretic media, the particles substantially block transmission of visible light through the display) and operate in a reflective mode, many electrophoretic displays can be made to operate in a so-called “shutter mode” in which one display state is substantially opaque and one is light-transmissive. See, for example, the aforementioned U.S. Pat. Nos. 6,130,774 and 6,172,798, and U.S. Pat. Nos. 5,872,552; 6,144,361; 6,271,823; 6,225,971; and 6,184,856. Dielectrophoretic displays, which are similar to electrophoretic displays but rely upon variations in electric field strength, can operate in a similar mode; see U.S. Pat. No. 4,418,346.
An encapsulated electrophoretic display typically does not suffer from the clustering and settling failure mode of traditional electrophoretic devices and provides further advantages, such as the ability to print or coat the display on a wide variety of flexible and rigid substrates. (Use of the word “printing” is intended to include all forms of printing and coating, including, but without limitation: pre-metered coatings such as patch die coating, slot or extrusion coating, slide or cascade coating, curtain coating; roll coating such as knife over roll coating, forward and reverse roll coating; gravure coating; dip coating; spray coating; meniscus coating; spin coating; brush coating; air knife coating; silk screen printing processes; electrostatic printing processes; thermal printing processes; ink jet printing processes; electrophoretic deposition (see US Patent Publication No. 2004/0226820); and other similar techniques.) Thus, the resulting display can be flexible. Further, because the display medium can be printed (using a variety of methods), the display itself can be made inexpensively.
As already noted, problems with the long-term image quality of conventional unencapsulated electrophoretic displays have hindered their widespread usage. For example, the electrophoretic particles tend to settle out of the fluid, resulting in inadequate service-life for these displays. Encapsulation of the electrophoretic internal phase (the electrophoretic particles and the surrounding fluid) avoids problems caused by large scale movement of the electrophoretic particles, since the electrophoretic particles can move only within the confines of an individual capsule, droplet or microcell. However, even in encapsulated electrophoretic displays, the stability of images written on the display is a matter of continuing concern. Although as already mentioned such displays do exhibit bistability, this bistability is not unlimited, and images on the display slowly fade with time. In the absence of an electric field, the electrophoretic particles of an encapsulated display tend to settle or slump under the influence of gravity, leading to objectionable changes in the optical state. Even where the density of the electrophoretic particles is similar to that of the surrounding fluid (and it is often difficult to find combinations of particles and fluids having similar densities and meeting all the other requirements required in electrophoretic displays), Brownian motion of the electrophoretic particles, and, in the case of electrophoretic media containing electrophoretic particle bearing charges of both polarities, electrostatic forces between oppositely-charged particles, can lead to degradation of an optical state, typically manifested as a gradual loss of contrast. Although the electrophoretic particles can only move within the confines of a single capsule, droplet or microcell, intermixing of two or more types of particles (in the case of electrophoretic media containing multiple types of particles) or movement of particle relative to a colored fluid (in electrophoretic media containing particles and such a colored fluid) can gradually degrade an image written on the display.
Several approaches have been suggested to reduce the aforementioned image-degrading effects, and thus to increase the bistability of an electrophoretic display. For example, it has been suggested that the particles and the walls of the surrounding capsule or microcell be chosen so that the particles are attracted to the walls. Such attraction can be electrostatic (when the electrochemical potentials of the surfaces of the particle and the wall are dissimilar), chemical, or dispersive (i.e., result from van der Waals forces) in nature. However such particle-wall forces typically stabilize only one layer of particles, which may be adequate if the particles are light absorbing (e.g., black), but will not be adequate for light scattering (e.g., white particles), where several layers of particles are necessary for adequate optical performance.
Another approach is to choose the electrophoretic particles and the fluid so that there is a weak attractive force between similar particles, i.e., so these particles are weakly flocculated when similar particles are aggregated together after writing an image on the display. This weak attractive force can be achieved in several different ways. For example, the aforementioned U.S. Pat. No. 7,170,670 describes an electrophoretic medium in which weak flocculation of particles is achieved by the addition to the fluid of a high molecular weight polymer, such as polyisobutylene, that is believed to cause depletion flocculation of the electrophoretic particles. Although this approach can give substantial improvements in bistability, the addition of the polymer to the fluid inevitably increases the viscosity of the fluid, and hence increases the switching time of the display, since the increased viscosity of the fluid reduces the rate of movement of the electrophoretic particles at any given electric field.
Accordingly, it is desirable to adopt an approach to increasing image bistability which can achieve electrophoretic particle flocculation without significant increase in the viscosity of the fluid. One such approach, described in the aforementioned U.S. Pat. No. 7,230,750, involves modification of the polymer shell which is advantageously present around electrophoretic particles (see the aforementioned U.S. Pat. No. 6,822,782) to promote inter-particle attraction. This modification comprises incorporation into the polymer shell of repeating units derived from a monomer the homopolymer of which is incompatible with the fluid, so that the added monomer tends to make the polymer shell less solvated by the fluid, and hence promote self-aggregation of similar electrophoretic particles. The aforementioned U.S. Pat. No. 7,230,750 shows that electrophoretic displays incorporating particles having such modified polymer shells possess improved image stability, and may have a threshold for switching, i.e., the medium does not change optical state until the applied electric field exceeds a certain threshold value.
U.S. Patent Application Publication No. 2004/0131959 describes a method for inducing or enhancing the threshold voltage of an electrophoretic display using a fluorinated fluid containing a “threshold promoter” comprising a halogenated group or a halogenated polymeric or oligomeric chain attached to one or more functional groups capable of hydrogen bonding, acid-base interaction, donor-acceptor interaction, metal-ligand interaction or Coulombic interaction. It appears from Paragraph 81 of this Publication that the function of the threshold promoter is to increase interaction between an electrode protecting layer of the display and the electrophoretic particles.
It has now been found that the bistability of an electrophoretic medium comprising polymer-coated electrophoretic particles dispersed in a fluid can be improved by providing appropriate groups in the polymer coating, and dispersing in the fluid a polymer having groups which can weakly interact with the groups in the polymer coating.